A synthesized cyclometalated palladium-azo complex was explored as a multifunctional probe for visual detection of SO2, H2S and NH3 in water. In acidic aqueous environment, the sensing solution underwent a sharp color...A synthesized cyclometalated palladium-azo complex was explored as a multifunctional probe for visual detection of SO2, H2S and NH3 in water. In acidic aqueous environment, the sensing solution underwent a sharp color change from poor violet to deep blue when titrated with Na2SO3 standard solution. But the color changed from poor violet to bright yellow when titrated with Na2S standard solution. In basic environment, the sensing solution rapidly changed to magenta when titrated by NH4Cl-NH3 standard buffer solution at high concentration. However, the color of sensing solution changed to blue when titrated by NH4Cl-NH3 standard buffer solution at low concentration although the pH was kept constant during the titration. Different species of these hazardous gases at environmentally relevant concentration levels were differentiated by independent optical signal outputs, and the interference from other inorganic ions commonly existing in water was very small.展开更多
A new cyclometalated platinum complex containing 2, 5-bis(naphthalene-1-yl)-1,3,4-oxadiazole ligand was synthesized and characterized. The UV-Vis absorptions and photoluminescent properties of the ligand and its plati...A new cyclometalated platinum complex containing 2, 5-bis(naphthalene-1-yl)-1,3,4-oxadiazole ligand was synthesized and characterized. The UV-Vis absorptions and photoluminescent properties of the ligand and its platinum complex were investigated. A characteristic metal-ligand charge transfer absorption peak at 439 nm in the UV spectrum and a strong emission peak at 625 nm in the photoluminescence spectrum were observed for this complex in dichloromethane. Cyclic voltammtry (CV) analysis shows that the EHOMO (energy level of the highest occupied molecular orbital) and ELUMO (energy level of the lowest unoccupied molecular orbital) of the platinum complex are about 、5.69 and 、3.25 eV, respectively, indicating that the oxadiazole-based platinum complex has a potential application in electrophosphorescent devices used as a red-emitting material.展开更多
Intracellular p H undertakes critical functions in various biological and pathological processes. It is important to monitor intracellular p H fluctuations for understanding physiological and pathological processes.He...Intracellular p H undertakes critical functions in various biological and pathological processes. It is important to monitor intracellular p H fluctuations for understanding physiological and pathological processes.Here, one aldehyde-bearing cyclometalated iridium(Ⅲ) complex([(4-pba)_(2)Ir(dcphen)]PF_(6), 4-pba = 4-(2-pyridyl) benzaldehyde, dcphen = 4,7-dichloro-1,10-phenanthroline, probe 1) was synthesized and used to track intracellular p H fluctuations. Probe 1 displayed p H-dependent luminescence property in p H range of 1.81–6.81 with an evaluated p Kavalue of 4.30 in BR buffer-DMSO(v:v = 99:1). An intramolecular hydrogen bonds assisted p H-responsive mechanism was proposed for the p H-responsive behavior of probe1. Probe 1 was successfully applied for imaging and tracking p H fluctuations in He La cells under external stimulation with fast response time, good photostability as well as low cytotoxicity and high cell permeability. This work demonstrates that aldehyde-bearing cyclometalated iridium(Ⅲ) complex can be used as alternative p H-responsive probe for real-time tracking intracellular p H fluctuations, which provides a strategy for the design of p H-responsive probe in versatile applications.展开更多
A new series of mono-cyclometalated square planar platinum(Ⅱ) complexes have been synthesized and the single-crystal X-ray structures of complex 1 and 2 have been determined.The complexes have the general formula ppy...A new series of mono-cyclometalated square planar platinum(Ⅱ) complexes have been synthesized and the single-crystal X-ray structures of complex 1 and 2 have been determined.The complexes have the general formula ppyPt(O^O),where ppy is 2-phenylpyridyl,and O^O is β-diketonate ancillary ligands with the acyl substituent group in position 3 of(D)-(+)-camphor.Although,like the many Pt(Ⅱ) complexes with square-planar geometry,these complexes have plane stacking modes in crystal structure,the sterically bulky camphor-derived groups compel extensive slipping of the molecular stacking planes,resulting in the negligible overlapping of the aromatic ring fragments between molecules and the considerable Pt-Pt distance.The resolved spectra and a little shifted emission in solid state of complexes show that there is significant reduction of π-π interactions and Pt-Pt interactions,and suggest these complexes may be good candidates for doped phosphorescent organic light emitting diodes(PhOLEDs) and even for nondoped PhOLEDs.展开更多
Six bis-tridentate and two tris-bidentate cyclometalated ruthenium complexes with a 1,2,3-triazole-containing ligand have been prepared and characterized. Single-crystal X-ray analyses of complexes [（MeOptpy）Ru（Bud...Six bis-tridentate and two tris-bidentate cyclometalated ruthenium complexes with a 1,2,3-triazole-containing ligand have been prepared and characterized. Single-crystal X-ray analyses of complexes [（MeOptpy）Ru（Budtab）]-（PF6） and [（Mebip）Ru（Budtab）]（PF6） are presented, where MeOptpy is 4′-p-methoxyphenyl-2,2′：6′,2＂-terpyridine, Budtab is the 2-deprotonated form of 1,3-di（N-n-butyl-l,2,3-triazol-4-yl）benzene, and Mebip is bis（N-methyl-ben-zimidazolyl）pyridine. The electronic properties of these complexes are probed by spectroscopic and electrochemical analyses. Time-dependent density functional theory calculations have been performed to assist the assignment of the absorption spectra.展开更多
The complexes [Pt2L2（μ-dppm）]（ClO4）2 （1） and {[Pt2L2（μ-dppm）Li（CH3CN）2]（ClO4）3}n （2）, where HL is 6-[4-（diethoxyphosphorylmethyl）phenyl]-2,2′-bipyridinyl and dppm is bis（diphenylphosphino）methane,...The complexes [Pt2L2（μ-dppm）]（ClO4）2 （1） and {[Pt2L2（μ-dppm）Li（CH3CN）2]（ClO4）3}n （2）, where HL is 6-[4-（diethoxyphosphorylmethyl）phenyl]-2,2′-bipyridinyl and dppm is bis（diphenylphosphino）methane, have been synthesized and characterized. In complex 1 the platinum（Ⅱ） center adopts a distorted square planar coordination geometry. The polymer 2 exhibits a ＂stairstep＂ configuration with one-dimensional Pt（Ⅱ）N^N^CPO- Li（Ⅰ）-OPC^N^ NPt（Ⅱ） mixed-metal units which are linked through dppm. Both complexes have metal-metal interaction with Pt- Pt distances of 3.325（2） and 3.1432（9） A, respectively, and display strong metal-metal-to-ligand charge-transfer （MMLCT） triplet state emission. The density-functional-theory calculation was used to interpret the absorption spectra of the complexes.展开更多
A series of luminescent cyclometalated platinum(II) complexes, (C^N^N)Pt(C≡CR) [HC^N^N=4 (4 tolyl) 6 phenyl 2,2′ bipyridine; R=4 chlorophenyl (1), phenyl (2) and 4 tolyl (3)], were synthesized, and their...A series of luminescent cyclometalated platinum(II) complexes, (C^N^N)Pt(C≡CR) [HC^N^N=4 (4 tolyl) 6 phenyl 2,2′ bipyridine; R=4 chlorophenyl (1), phenyl (2) and 4 tolyl (3)], were synthesized, and their spectroscopic properties have been examined. These complexes are brightly emissive both in fluid solution and in the solid state, attributed to triplet metal to ligand charge transfer ( 3MLCT) state. The excited state energy can be tuned by ancillary acetylide ligands. The emission lifetimes in dichloro^methane solution at room temperature were up to 1 64 μs and the emission quantum yields were in the range of 0 03-0 15.展开更多
Organoplatinum（Ⅱ） compounds have received enormous attention over the past decades due to their square-planar geometry as well as intriguing photo-physical properties.Self-assembly has emerged as an excellent appro...Organoplatinum（Ⅱ） compounds have received enormous attention over the past decades due to their square-planar geometry as well as intriguing photo-physical properties.Self-assembly has emerged as an excellent approach to create well-ordered supramolecular architectures with tunable properties,which underpin the role of solvent-directed approach for the design of functional materials.In this minireview,the recent advances on supramolecular self-assembly of cyclometalated platinum（Ⅱ） complexes have been discussed.During the self-assembly process,non-covalent Pt-Pt and π-π interactions play crucial roles in controlling the structures and functions of the resulting assemblies.展开更多
We have theoretically investigated two series of cyclometalated Pt（II） complexes, a series [Pt （C, N, N） Cl] and b series [Pt （C, N, Npyrazolyl） Cl]. The geometrical and electronic structures are calculated at t...We have theoretically investigated two series of cyclometalated Pt（II） complexes, a series [Pt （C, N, N） Cl] and b series [Pt （C, N, Npyrazolyl） Cl]. The geometrical and electronic structures are calculated at the ECP60MWB//6-31G＊（H, C, Cl, N, S） basis set level using DFT method; one-photon absorption （OPA） properties are calculated by using both TDDFT and ZINDO methods and two-photon absorption （TPA） properties are obtained with the ZINDO/SOS method. The resonance integrals parameters （βsp and βd） for Pt are adjusted to -1 and -28.5 eV, respectively, to make max OPA wavelength calculated by ZINDO closest to the experimental data and TDDFT results. The calculated results indicate the molecule 2b （[Pt （Cnaphthyl, N, Npyrazolyl） Cl]） has the biggest potential as outstanding TPA materials because （i） the TPA properties of b series are more outstanding in IR wavelength range, the molecules in b series have good transparencies and possess 1-pyrazolyl-NH that is also available for another metal coordination （e.g., dimerization） and chemical interactions; （ii） when C is CnaphthyI in the C, N, N ligand of cyclometalated Pt（II） complexes, the molecules have the best conjugation effect and the best TPA properties.展开更多
基金Project supported by the National Natural Science Foundation of China （No. 20275033） and the Natural Science Foundation of Fujian Province of China （No. 2006J0173）.
文摘A synthesized cyclometalated palladium-azo complex was explored as a multifunctional probe for visual detection of SO2, H2S and NH3 in water. In acidic aqueous environment, the sensing solution underwent a sharp color change from poor violet to deep blue when titrated with Na2SO3 standard solution. But the color changed from poor violet to bright yellow when titrated with Na2S standard solution. In basic environment, the sensing solution rapidly changed to magenta when titrated by NH4Cl-NH3 standard buffer solution at high concentration. However, the color of sensing solution changed to blue when titrated by NH4Cl-NH3 standard buffer solution at low concentration although the pH was kept constant during the titration. Different species of these hazardous gases at environmentally relevant concentration levels were differentiated by independent optical signal outputs, and the interference from other inorganic ions commonly existing in water was very small.
基金Project(50473046) supported by the National Natural Science Foundation of ChinaProject(204097) supported by the Science Foundation of the Ministry of Education of China+1 种基金Project(04JJ1002) supported by the Outstanding Youth Foundation of Hunan Province,ChinaProject(06JJ2008) supported by the Natural Science Foundation of Hunan Province,China
文摘A new cyclometalated platinum complex containing 2, 5-bis(naphthalene-1-yl)-1,3,4-oxadiazole ligand was synthesized and characterized. The UV-Vis absorptions and photoluminescent properties of the ligand and its platinum complex were investigated. A characteristic metal-ligand charge transfer absorption peak at 439 nm in the UV spectrum and a strong emission peak at 625 nm in the photoluminescence spectrum were observed for this complex in dichloromethane. Cyclic voltammtry (CV) analysis shows that the EHOMO (energy level of the highest occupied molecular orbital) and ELUMO (energy level of the lowest unoccupied molecular orbital) of the platinum complex are about 、5.69 and 、3.25 eV, respectively, indicating that the oxadiazole-based platinum complex has a potential application in electrophosphorescent devices used as a red-emitting material.
基金supported by the National Natural Science Foundation of China (Nos. 22074087, 21804106 and 11727813)the Fundamental Research Funds for the Central Universities (No. 2021TS032)。
文摘Intracellular p H undertakes critical functions in various biological and pathological processes. It is important to monitor intracellular p H fluctuations for understanding physiological and pathological processes.Here, one aldehyde-bearing cyclometalated iridium(Ⅲ) complex([(4-pba)_(2)Ir(dcphen)]PF_(6), 4-pba = 4-(2-pyridyl) benzaldehyde, dcphen = 4,7-dichloro-1,10-phenanthroline, probe 1) was synthesized and used to track intracellular p H fluctuations. Probe 1 displayed p H-dependent luminescence property in p H range of 1.81–6.81 with an evaluated p Kavalue of 4.30 in BR buffer-DMSO(v:v = 99:1). An intramolecular hydrogen bonds assisted p H-responsive mechanism was proposed for the p H-responsive behavior of probe1. Probe 1 was successfully applied for imaging and tracking p H fluctuations in He La cells under external stimulation with fast response time, good photostability as well as low cytotoxicity and high cell permeability. This work demonstrates that aldehyde-bearing cyclometalated iridium(Ⅲ) complex can be used as alternative p H-responsive probe for real-time tracking intracellular p H fluctuations, which provides a strategy for the design of p H-responsive probe in versatile applications.
基金support from the National Natural Science Foundation of China (Grant No. 20472060)the Basic Research Foundation of Sichuan Province,China (Grant No. 07JY029-015)
文摘A new series of mono-cyclometalated square planar platinum(Ⅱ) complexes have been synthesized and the single-crystal X-ray structures of complex 1 and 2 have been determined.The complexes have the general formula ppyPt(O^O),where ppy is 2-phenylpyridyl,and O^O is β-diketonate ancillary ligands with the acyl substituent group in position 3 of(D)-(+)-camphor.Although,like the many Pt(Ⅱ) complexes with square-planar geometry,these complexes have plane stacking modes in crystal structure,the sterically bulky camphor-derived groups compel extensive slipping of the molecular stacking planes,resulting in the negligible overlapping of the aromatic ring fragments between molecules and the considerable Pt-Pt distance.The resolved spectra and a little shifted emission in solid state of complexes show that there is significant reduction of π-π interactions and Pt-Pt interactions,and suggest these complexes may be good candidates for doped phosphorescent organic light emitting diodes(PhOLEDs) and even for nondoped PhOLEDs.
文摘Six bis-tridentate and two tris-bidentate cyclometalated ruthenium complexes with a 1,2,3-triazole-containing ligand have been prepared and characterized. Single-crystal X-ray analyses of complexes [（MeOptpy）Ru（Budtab）]-（PF6） and [（Mebip）Ru（Budtab）]（PF6） are presented, where MeOptpy is 4′-p-methoxyphenyl-2,2′：6′,2＂-terpyridine, Budtab is the 2-deprotonated form of 1,3-di（N-n-butyl-l,2,3-triazol-4-yl）benzene, and Mebip is bis（N-methyl-ben-zimidazolyl）pyridine. The electronic properties of these complexes are probed by spectroscopic and electrochemical analyses. Time-dependent density functional theory calculations have been performed to assist the assignment of the absorption spectra.
文摘The complexes [Pt2L2（μ-dppm）]（ClO4）2 （1） and {[Pt2L2（μ-dppm）Li（CH3CN）2]（ClO4）3}n （2）, where HL is 6-[4-（diethoxyphosphorylmethyl）phenyl]-2,2′-bipyridinyl and dppm is bis（diphenylphosphino）methane, have been synthesized and characterized. In complex 1 the platinum（Ⅱ） center adopts a distorted square planar coordination geometry. The polymer 2 exhibits a ＂stairstep＂ configuration with one-dimensional Pt（Ⅱ）N^N^CPO- Li（Ⅰ）-OPC^N^ NPt（Ⅱ） mixed-metal units which are linked through dppm. Both complexes have metal-metal interaction with Pt- Pt distances of 3.325（2） and 3.1432（9） A, respectively, and display strong metal-metal-to-ligand charge-transfer （MMLCT） triplet state emission. The density-functional-theory calculation was used to interpret the absorption spectra of the complexes.
文摘A series of luminescent cyclometalated platinum(II) complexes, (C^N^N)Pt(C≡CR) [HC^N^N=4 (4 tolyl) 6 phenyl 2,2′ bipyridine; R=4 chlorophenyl (1), phenyl (2) and 4 tolyl (3)], were synthesized, and their spectroscopic properties have been examined. These complexes are brightly emissive both in fluid solution and in the solid state, attributed to triplet metal to ligand charge transfer ( 3MLCT) state. The excited state energy can be tuned by ancillary acetylide ligands. The emission lifetimes in dichloro^methane solution at room temperature were up to 1 64 μs and the emission quantum yields were in the range of 0 03-0 15.
基金supported by the National Natural Science Foundation of China(No.21274139)the Fundamental Research Funds for the Central Universities(Nos.WK3450000001,WK2060200012)
文摘Organoplatinum（Ⅱ） compounds have received enormous attention over the past decades due to their square-planar geometry as well as intriguing photo-physical properties.Self-assembly has emerged as an excellent approach to create well-ordered supramolecular architectures with tunable properties,which underpin the role of solvent-directed approach for the design of functional materials.In this minireview,the recent advances on supramolecular self-assembly of cyclometalated platinum（Ⅱ） complexes have been discussed.During the self-assembly process,non-covalent Pt-Pt and π-π interactions play crucial roles in controlling the structures and functions of the resulting assemblies.
基金supported by the Youth Scholar Backbone Supporting Plan Project for General Universities of Heilongjiang Province (1155G22)China Postdoctoral Science Foundation (20100481018)+2 种基金Heilongjiang Postdoctoral Financial Assistance (LBH-Z09096)Youth Science Foundation of Harbin University of Science and Technology (2009YF020)National Natural Science Foundation of China (20973078)
文摘We have theoretically investigated two series of cyclometalated Pt（II） complexes, a series [Pt （C, N, N） Cl] and b series [Pt （C, N, Npyrazolyl） Cl]. The geometrical and electronic structures are calculated at the ECP60MWB//6-31G＊（H, C, Cl, N, S） basis set level using DFT method; one-photon absorption （OPA） properties are calculated by using both TDDFT and ZINDO methods and two-photon absorption （TPA） properties are obtained with the ZINDO/SOS method. The resonance integrals parameters （βsp and βd） for Pt are adjusted to -1 and -28.5 eV, respectively, to make max OPA wavelength calculated by ZINDO closest to the experimental data and TDDFT results. The calculated results indicate the molecule 2b （[Pt （Cnaphthyl, N, Npyrazolyl） Cl]） has the biggest potential as outstanding TPA materials because （i） the TPA properties of b series are more outstanding in IR wavelength range, the molecules in b series have good transparencies and possess 1-pyrazolyl-NH that is also available for another metal coordination （e.g., dimerization） and chemical interactions; （ii） when C is CnaphthyI in the C, N, N ligand of cyclometalated Pt（II） complexes, the molecules have the best conjugation effect and the best TPA properties.
